New primary disazo dyestuffs



Patented Sept 30, 1930 UNITED 'STATE-S PATENT OFFIE JAMES BADDILEY, PERCY OHORLEY, AND RAINALD BRIGHTMAN, or BLACKLEY, MA1\l'- CHESTER, ENGLAND, ASSIGNORS TO BRITISH DYESTUFFS CORPORATION LIMITED,

OF BLACKLEY, MANCHESTER, ENGLAND NEW PRIMARY DISAZO DYESTUEFS No Drawing. Application filed. April 19, 1928 Serial 'No. 271,399, and. in Great Britain April 28, 1927.

According to thisinvention We obtain new and valuable dlsazo dyestuffs by comblmng meta monomtro-benz dine or m-m-d1mtrobenzidme having the respect ve formulae with one molecule of an amino naphthol sulphonic acid or an N -substituted derivative thereof and one molecule of any of the usual coupling components. These new dyestuffs may be represented by the following probable general formula IIIOz R:

cule of 2-aminor8-naphthol-6-sulphonic acid or an.Nsubstituted.derivative thereof; that isa .Z-amino-B-naphthol-6-sulphonic acid of the general type v H i The amino naphthol sulphonic acid may be combined eitherin acid orin alkalinesolution, and it maybe combined before or after combination With the other coupling componehtL. y V V p q The present invention relates'to a broad class of dyes.v There" are hereinafter given many specific examples showing the various couphng components that are typical illustrations, which may be coupled with the tetrazotized meta nitrated benzidine compound. By the choice of the specific coupling coniponent and the manner of coupling dyes of various shades maybe prepared. Thepresent invention is susceptible of considerable modification without exceeding the broad scope as indicated above.

The following examples illustrate the invention without limiting it, parts being by Weight:

Ewample 15-229 parts of meta mononitrobenzidine are 'tetrazotized With 138 parts of sodium nitrite in the usual way and the suspension of tetrazo compound is stirred into a cold solution of l38 parts of salicylic acid in 40 parts of sodium hydroxide containing 400 parts of sodiumcarbonate. The mixture is cooled with ice and stirred until coupling is complete, when a solution of 239 parts of l amino-S-naphthOl- L-Sulphonic acid in 4:0

The

parts of sodium hydroxide is added. mlxture .1s' stirred and maintained alkaline until coupling is complete, when it is heated up and the dyestutlf isolated by the addition of common salt. It dyes viscose silk in even violet-brown shades and wool a brownishviolet shade, fast to milling.

' E'zmmple 2.=The suspension of tetrazo compound obtained by treating 229 parts of meta.mononitrobenzidine with 138 parts 01' sodium nitrite and 500 parts of 36% hydroi chloric acid is stirred into a solution of 138 parts of sal'icyclic acid in 40 parts of sodiun r h droxide containin 4-00 oarts of sodium y n 1 carbonate.

solution containing 239 parts of 2-amino-8- naphthOl-G-sulphonic acid is stirred in; .After stirring the acid mixture until combinationis complete, the mixture 1s made allza- Stirring is continued until coue .pli'ngis complete'when the mixture is made acid by means of acetic acid and a neutral line, heated up and the dyestuff isolated by the addition of common salt. It dyes viscose silk and wool in red shades.

Example 3.-229 parts of meta mononitrobenzidine are tetrazotized with 138 parts of sodium nitrite in the usual way and to the suspension of tetrazo compound there is added a neutral solution of 323 parts ot' 1 2 5-dichloro-4c sulphophenyl- 3 -methyl- 5-pyra-zolone. The mixture is stirred until coupling is complete, when it is rendered alkaline by the addition of sodium carbonate and aneutral solution of 2-amino-8-naphthol-t-sulplionic acid is. stirred in. Stirring is continued until coupling is complete, when the mixture is heated up and the dyestufi' isolated by the addition of common salt. It dyes viscose silk a yellow-brown shade and wool in yellowish-brown shades fast to milling. A dyestutt' giving somewhat redder shades is obtained by adding to the suspension of tetrazo' compound, first the neutral solution of 2-amino-8-naphthol-(i-sulphonic acid and about 250 parts of sodium acetate crystals, and then a neutral solution of 25% parts of 1:para-sulphophenyl 3-mcthyl-5- pyrazolone and stirring until coupling is complete, after which the mixture is made alkaline and the 'dyestuff isolated in the usual way.

Eaample 4. 229 parts of meta mononitrobenzidine are tetrazotized with 138 parts of sodium nitrite in the usual way and to the suspension of tetrazo compound there 1s added a neutral solution of 2 15 parts of sodium naphthionate. Alkali is added to remove most of the acidity and the faintly acid mixture is stirred until coupling is complete. The mixture is then made alkaline with sodium carbonate and a neutral solution of 337 parts of the sodium salt of 2-phenylamino-8-naphthol-G-sulphonic acid is added.

After stirring until coupling is complete, the

mixture is heated up and the dyestulf isolated by the additionof common salt. It dyes viscose a maroon shade and wool a copperbrown shade.

E wample 5.-229 parts of meta mononitrobenzidine are tetrazotized in the usual way with 138 parts of sodium nitrite, and. the

suspension of tetrazo compound is SillIlGtl into a solution of 239 parts of 2-amino-8- naphthol-6-sulphonic acid, containing 350 parts of soda ash. The mixture is stirred until coupling is complete, when a solut on of parts of reso-rcinol is added. The mixture is maintained alkaline and stirred until coupling is complete, when it is heated up and the dyestu'li isolated by the addition of common salt. It dyes viscose silk in violet-brown shades and wool in violet-brown shades.

A dyestufl affording very similar SlllClBS'lS obtained by using a solution of 108 parts of metaphenylenediamine in place of the solu- '1,776,soi

tion of resorcinol used in the above example. If in place of a solution of metaphenylene diamine or resorcinol in the above example, there is added a neutral solution of 224-. parts of 1-naphthol-4-sulphonic acid, the coupling medium being alkaline throughout, we obtain a dyestuii' dyeing viscosesilk a brownishviolet and wool a chill violet shade. Similarly, by adding a neutral solution containing a further 239 parts of :2-amino-S-naphthol-(S- sulphonic acid, in place of the l-naphthollsulphonic acid, there is obtained a dyestuil' dyeing viscose silk a claret shade and wool a reddish-brox'vn shade. Ewample 6.274 parts of 2:2-dinitrobenzidine aredissolved in water with 500 parts of 36% hydrochloric acid and tetrazotized by treating with 138 parts of sodium nitrite. The suspension of yellow-brown tetrazo compound is stirred into a solution containing 138partsof'salicylic acid and 500 parts of sodium carbonate. After stirring about an hour a neutral solution containing 239 parts of 2-amino S-naphthol-ti-sulpl'ionic acid is added. Stirring is continued until combination is completed when the mixture is heated up and the dyestulf is isolated by the addition of common salt. It dyes viscose silk a yellowish-brown shade.

E wample /".229 parts of meta-mononitrobenzidine are tetrazotized and combined in alkaline medium with 138 parts of salicylic acid as-described in Example 1. After this coupling is completed aneutral solution of 239 parts of 2-amino-8-naphthol-(S-sulphonic acid is add-ed and the alkaline mixture is stirred until coupling is complete. The mixture is then heated upand the dyesturf isolated by addition of salt. lVhen dry it forms agrey-blackpowder dissolving in water to a red-brown solution which is not changed on addition of alkalies but deposits a red precipitate on addition of mineral acid. The powder dissolved instrong-sulphuric acid to a crimson solution which deposits a redbrown precipitate on dilution. The dyestuff' dyes viscose silk a reddish-brown shade.

ExampZe'8.229 parts of meta-mononitrobenzidine are tetrazotized and combined in alkaline medium with 138 parts of salicylic 'acid as described in Example 1. After this coupling is completed aneutral solution of 315 parts of Q-phenylamino-8-naphthol-6- sulphonic acid is added and the alkaline mixture is stirred until coupling is complete. The mixture is then heated up and the dyestulf isolated by addition of salts. WVhen dry itiorms a grey-black powder dissolving in water to a. dark brown solution which becomes redder on addition of caustic soda and deposits a brown'precipitat'e on addition of mineral acids. The powder dissolves in strong sulphuric acid to a crimson solution which deposits a red-brown precipitate on dilution. The dyestufi" dyes viscose silk a of anaminonaphtholsulphonic acid of the brown shade.

Our invention is further illustrated by the examples quoted in the following table, in which the diazo component in each case is tetrazotized 2-nitrobenzidine:

Second coupling compon- First coupling ent (coupled alkaline i Shade on viscose component unless otherwise stated) silk Salicylic acid 2 phenylamino 5 Red naphthol 7-- sulphonic acid I r Do 5 hydroxy 2 naphthyl- Yellowish-red glycine 7 sulplionic acid Do 2 benzoylamino 8 Scarlet naphthol G sulphonic acid Do 8 hydroxy 2 naphthyl- Brown glycine 6 sulphonic aci 7 Do 2 ethylamino 8 naph-' Brown thol 6 sulphonic acid Do 2 2 4 dinitrophenyl- 'Reddish-brown amino 8 naphthol- 6 sulphonic acid Do 2 (4 chlorophenyl- Brown amino) 8 naphthol- (i-sulphonic acid o-cresotinic acid 2 m xylylamino 8 Brown naphthol 6 sulphonic acid Beta oxynaphthoic 2 amino 8 naphthol 6 Reddish-violet acid sulphonic acid Salicylic acid 2 m xylylamino 8 Brown naphthol -,.6 sulphonic acid o-cresotinic acid 2' phenylamino 8 Brown naphthol 6 sulphonic acid p-cresotinic acid 2 phenylamino 8 napl1- Brown 7 thol-G -sulphonic acid o-cl'esotinic acid 2 amino S-naphthol 6- Yellowish-brown sulphonic acid p-cresotinic acid 2 amino 8 naphthol 6- Yellowish-brown sulphonic acid 1 1 phenyl 3 2 amino 8 -naphthol 6- Bluish-brown methyl 5 pyrasulphonic acid zolone I 1 phenyl 3 2- amino 8 -naphtho1- 6 Crimson methyl 5 pyrazolone sulphonic acid (acid coupled) The 2.- l-chlorophenylamino) -8-naphthol-6-sulphonic acid used as a coupling component in some of the above examples may be made b-y condensing p-chloroani-' tetrazotizing meta nitrated benzidine and coupling the tetrazo compound'with one molecular proportion of any coupling component and with one molecular proportion of an aminonaphthol sulphonic acid, the products being brown to black powders, which dissolve in water giving red-brown to violet-brown solutions and yield crimson-red to dull violet or violet-brown solutionsin sulphuric acid, dyeing viscose silk in shades varying from yellowish-brown andred to Violet-brown,

2. New primary disazo dyes obtained by tcti-azotizing a meta nitrated benzidine and coupling the tetrazo compound with onemolecular proportion'ofjany coupling component and with one imolecular proportion formula in whichhydrogen and aryl groups are both represented by R the products being brown to black powders, which dissolve in water giving red-brown to violet-brown solutions and yield crimson-red to dull violet or Violetbrown solutions in sulphuric acid, dyeing viscose silk in shades varying from yellowishbrown and red to'violet-brown.

3. New primary disazo dyes obtained by tetrazotizing a meta nitrated benzidine and coupling the tetrazo compound with one in which hydrogen and aryl groups are both representedby H the products being brown to black powders, which dissolve in water giving red-brown to violet-brown solutions and yield crimson-red todull violet or Violetbrown solutions in sulphuric acid, dyeing viscose silk in shades Varying from yellow-.

ish-brown and red to violet-brown.

4. Asnew dyes the disazo dyes having the probable general formula r wherein R represents hydrogen or a nitro group and R and R represent coupling components, one of which is an amino naphthol,

sulphonic acid, the said dyes being soluble in water and in sulphuric acid and dyeing wool and viscose silk in level shades, the said dyes being obtainable by coupling a tetrazotized meta nitrated benzidine with one molecular proportion of a coupling component and one molecular proportion of an-amino naphthol sulphonic acid.

5. As new dyes the disazo dyes having the probable general formula 1 whereinv R represents hydrogen or a nitro group and R and R represent coupling components, one of which is an amino naphthol sulphonic acid of the type V wherein R represents hydrogen, alkyl, acyl or aryl groups, the said dyes being soluble in Water and sulphuric acid and dyeing wool and Viscose silk in level shades, the said dyes being obtainable by coupling a tetrazotized meta nitrated' benzidine with one molecular proportion of a coupling component and one molecular proportion of the said amino naphthol sulphonic acid.

' 6. As new dyes the disazo dyes having the probable general formula wherein R represents hydrogen or a nitro group and R- and R represent coupling components, one coupling component being an ortho hydroxycarboxylic acid of the benzene series and the other coupling component being an amino naphthol sulphonic acid, the said dyes being soluble in water and in sulphuric acid and dyeing wool and viscose silk in level shades, the said dyes being obtainable by coupling a tetrazotized meta nitrated benzidine with one molecular proportion of said ortlio hydroxycarboxylic acid and one molecular proportion of said amino naphthol sulphonic acid.

7. Asfnew dyes the disazo dyes having the probable general formula 'wherein R represents hydrogen or a nitro group and R and R represent couplin g components, one coupling component being an -ortho hydroxycarboxylic acid of the other benzene series and the coupling component being an am no naphthol sulphonic acid of the type i r wherein R represents hydrogen, alkyl, acyl or aryl groups, the said dyes being soluble in water and in sulphuric acid and dyeing wool and viscose silk in level shades, the said dyes being obtainable by coupling a tetrazotize-d meta nitrated benzidine with one molecular proportion of said ortho hydroxy- Hoiscarboxylic acid and withone molecular proportion of the said amino naphthol sulphonic acid.

8. As new dyes the disazo-dyes having the probable general formula having the wherein R represents hydrogen or a nitro group and R and R represent coupling components, one coupling component being salicylic acid and the other coupling component being an amino naphthol sulphonic acid of the type wherein R represents hydrogen, alkyl, acyl or aryl groups, the said dyes being soluble in water and in sulphuric acid and dyeing wool and viscose silk in level shades, the said dyes being obtainable by coupling a tetrazotized meta nitrated benzidine with one molecular proportion of said salicylic acid and one molecular proportion of the said amino naphthol sulphonic acid.

10. As new dyes the disazo dyes having the probable general formula wherein R and R represent coupling components, one of which is an ammo naphthol sulphonic acid, the said dyes being soluble in water and in sulphuric acid and dyeing wool and viscose silk in level shades, the said dyes being obtainable by coupling a tetrazotized meta mono nitrated benzidine with one molecular proportion of a coupling component and one molecular proportion of an amino naphthol sulphonic acid.

11. As new dyes the disazo dyes having the probable general formula wherein R and R represent coupling components, one of whlch 1s an am no naphthol sulphonlc ac1d of the type wherein R represents hydrogen, alkyl, acyl or aryl groups, the said dyes being soluble in water and in sulphuric acid and dyeing wool and Viscose silk in level shades, the said dyes being obtainable by coupling a tetrazotized meta mono nitrated benzidine with one molecular proportion of a coupling component and one molecular proportion of the said amino naphthol sulphonic acid.

12. As new dyes the disazo dyes having the probable general formula wherein R and R represent coupling components, one coupling component being an ortho hydroxycarboxylic acid of the benzene series and the other coupling component besaid dyes being soluble in water and in sulphuric acid and dyeing wool and viscose silk in level shades, the said dyes being obtainable by coupling a tetrazotized meta mono nitrated benzidine with one molecular proportion of said ortho hydroxycarboxylic acid and one molecular proportion of said amino naphthol sulphonic acid.

18. As new dyes the disazo dyes having the probable general formula NOg wherein R and R represent coupling components, one coupling component being an ortho hydroXycarboXylic acid of the other benzene-series and the coupling component being an amino naphthol sulphonic acid of the type I NRs HOaS wherein R represents hydrogen, alkyl, acyl or aryl groups, the said dyes being soluble in water and in sulphuric acid and dyeing wool and viscose silk in level shades, the said dyes being obtainable by coupling a tetrazotized meta mono nitrated benzidine with one molecular proportion of said ortho hydroXyc-arboxylic acid and with one molecular proporlllqlgl of the said amino naphthol sulphonic ac1 14:. As new dyes the disazo dyes having the probable general formula I'Vth wherein R and R represent coupling components, one coupling component being salicylic acid and the other coupling component being an amino naphthol sulphonic acid of the type ing an amino naphthol sulphonic acid, the

wherein R represents hydrogen, alkyl, acyl or aryl groups, the said dyes being soluble in water and in sulphuric acid and dyeing wool and viscose silk in level shades, the said dyes being obtainable by coupling a tetrazotized meta mono nitrated benzidine with one 1110- lecular proportion of said salicylic acid and one molecular proportion of the said amino naphthol sulphonic acid.

In testimony whereof we aifix our signatures.

JAMES BADDILEY. PERGY CHOR-LEY.

RAINALD BRIGHTMAN. 

